The instant invention pertains to photostable, silylated benzotriazole UV absorbers and compositions stabilized therewith. These benzotriazole compounds are novel and exhibit enhanced durability due to either the incorporation of electron withdrawing moieties at the 5-position of the benzo ring or to the presence of an xcex1-cumyl group on the phenol ring. The polymer compositions containing said benzotriazoles are advantageously stabilized, especially high performance coatings such as organopolysiloxanes. The instant compounds are red-shifted and show increased absorption in the 350-400 nm region of the UV spectrum.
Copending patent application Ser. No. 08/981,433, now U.S. Pat. No. 6,005,036, describes polysiloxanes themselves which are useful as process stabilizers.
U.S. Pat. No. 4,859,759 describes in the most generic manner siloxane compounds containing at least one benzotriazole and one hindered amine substituent covalently coupled to a silicon atom. This reference does not supply any specific exemplification of such structures. The particular structures of the instant invention are neither disclosed nor suggested by this reference.
U.S. Pat. Nos. 5,707,690 and 5,756,793 disclose the use of silylated benzophenones for the protective coatings for wood. EP 675,108 B1 describes thioether substituted benzophenone UV absorbers which may also contain silylated substituents.
U.S. Pat. Nos. 5,185,445 and 5,837,792 describe polysiloxane light stabilizers which contain pendant hydroxyphenyl-diaryl-s-triazine moieties.
U.S. Pat. Nos. 5,219,905; 5,321,066; 5,418,267; 5,463,058 and 5,578,665 disclose hindered amines containing siloxane and other silyl moieties as stabilizers.
U.S. Pat. Nos. 5,391,795 and 5,679,820 describe the preparation and use of silylated benzophenone UV absorbers. U.S. Pat. No. 5,391,795 compares these silylated benzophenone UV absorbers with one example of a silylated benzotriazole UV absorber which is 2-{2-hydroxy-5-[3-(3-triethoxysilyl)propylcarbamoyloxy]propylphenyl}2H-benzotriazole. This silylated benzotriazole compound contains neither a bulky substituent ortho to the hydroxy group in the phenyl ring nor an electron withdrawing group at the 5-position of the benzo ring. Both of these two substitution patterns are shown to be particularly efficacious in enhancing long term photostability of the benzotriazoles. The electron withdrawing group at the 5-position of the benzo ring allows for the red-shifting of the UV spectrum of the benzotriazoles.
U.S. Pat. No. 4,373,061 teaches the use of silicone coatings for unprimed plastic substrates and coated articles. The silicone coating contains a UV absorbing organic group attached to silicon by carbon-silicon bonds. The UV absorber is a silylated hydroxy-benzophenone.
U.S. Pat. No. 4,322,455 describes a process for producing an ultraviolet radiation stabilized polymeric article which contains on the surface of said article a UV absorbing composition. The UV absorber may be generically any of the known types of compounds such as benzophenones, benzotriazole, cyanoacrylates or benzylidene malonates. The only benzotriazole disclosed is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole.
Copending application Ser. No. 09/234,880, now U.S. Pat. No. 6,166,218, demonstrates the value of having such substitution at the 3-position of the phenyl ring by a bulky group and at the 5-position of the benzo ring by an electron withdrawing moiety. All the instant compounds have an electron withdrawing moiety at the 5-position of the benzo ring. When there is a bulky substituent at the 3-position of the phenyl ring, particularly an xcex1-cumyl group, the photostability of the benzotriazole is particularly enhanced.
The first object of this invention is to provide for new monomeric benzotriazole UV absorbers which contain silicon moieties.
Another object of this invention is to provide silicone/siloxane hardcoat or softcoat resin compositions containing said benzotriazole UV absorbers which can be added to or copolymerized into such hardcoat or softcoat resins.
Still another object of the invention is to provide for articles which contain the siliconelsiloxane hardcoat or softcoat composition as a screening layer in a laminate composition, such as over polycarbonate.
Another object of the invention is provide automotive coating compositions which the instant compounds are melamine/siloxane crosslinked structures.
Still another object of the invention is to provide for polymer compositions where the instant compounds are used in conjunction with silylated hindered amines including inter alia N-hydrocarbyloxy and N-hydroxyalkyloxy substituted hindered amines.
Still another object of the invention is to provide for silicone/siloxane hardcoat or softcoat compositions containing post-added other advanced benzotriazoles which do not contain silicon moieties and with or without the concomitant presence of hindered amines, N-hydrocarbyloxy- or N-hydroxyalkyloxy-substituted hindered amines.
The instant invention pertains to benzotriazole compounds of formula (I) or (II) 
wherein
G1 and G6 are independently hydrogen or halogen;
G2 and G7 are independently cyano, perfluoroalkyl of 1 to 12 carbon atoms, fluoro, chloro, xe2x80x94COxe2x80x94G3, xe2x80x94COOG3, xe2x80x94CONHG3, xe2x80x94CON(G3)2, E3SOxe2x80x94, E3SO2xe2x80x94, xe2x80x94PO(C6H5)2, 
Oxe2x80x94COxe2x80x94NHxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n or xe2x80x94COxe2x80x94Xxe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n;
or G7 is also hydrogen;
or G2 may also be hydrogen when E1 is a group of formula (IV) or (V);
T1 and T2 are independently alkylene of 1 to 18 carbon atoms, preferably alkylene of 2 or 3 carbon atoms, or alkylene-phenylene-alkylene of 8 to 20 carbon atoms;
R1 and R2 are independently alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 10 carbon atoms or phenylalkyl of 7 to 20 carbon atoms, preferably alkyl of 1 to 6 carbon atoms or phenyl;
n is 0, 1, 2 or 3;
X is xe2x80x94Oxe2x80x94, xe2x80x94NE4xe2x80x94 or xe2x80x94NHxe2x80x94;
G3 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms;
E1 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms or by one or more of the following groups xe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94Xxe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n, or xe2x80x94Xxe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n;
or E1 is alkyl of 1 to 24 carbon atoms substituted by one or two hydroxy groups;
or E1 is a group of formula (IV) or (V) 
where
E27 and E28 are independently alkyl of 1 to 18 carbon atoms, or cycloalkyl of 5 to 12 carbon atoms;
E22, E23, E24, E25 and E26 are independently hydrogen, halogen, straight or branched alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, said alkyl or said alkenyl substituted by one or more halogen, xe2x80x94OCOE11, xe2x80x94OE4, xe2x80x94NCO, xe2x80x94NHCOE11, or xe2x80x94NE7E8, or mixtures thereof, where E4 is straight or branched chain alkyl of 1 to 24 carbon atoms or straight or branched chain alkenyl of 2 to 18 carbon atoms; or said alkyl or said alkenyl interrupted by one or more xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94NE4xe2x80x94 groups or mixtures thereof and which can be unsubstituted or substituted by one or more xe2x80x94OH, xe2x80x94OE4 or xe2x80x94NH2, or mixtures thereof; or
E22, E23, E24, E25 and E26 are independently phenyl, xe2x80x94OH, xe2x80x94OCOE11, xe2x80x94OE29, xe2x80x94NCO, xe2x80x94NHCOE11, or xe2x80x94NE7E8, cyano, nitro, perfluoroalkyl of 1 to 12 carbon atoms, xe2x80x94COG3, xe2x80x94COOG3, xe2x80x94CON(G3)2, xe2x80x94CONHG3, E3Sxe2x80x94, E3SOxe2x80x94, E3SO2xe2x80x94, xe2x80x94P(O)(C6H5)2, xe2x80x94P(O))OG3)2, xe2x80x94SO2xe2x80x94X1xe2x80x94E29;
X1 is xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94NE4xe2x80x94;
E29 is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, said alkyl or said alkenyl substituted by one or more xe2x80x94OH, xe2x80x94OCOE11, xe2x80x94OE4, xe2x80x94NCO, xe2x80x94NHCOE11, xe2x80x94NE7E8, phthalimido, 
or mixtures thereof, where E4 is straight or branched chain alkyl of 1 to 24 carbon atoms or alkenyl of 2 to 18 carbon atoms; or said alkyl or said alkenyl interrupted by one or more xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94NE4xe2x80x94 groups or mixtures thereof and which can be unsubstituted or substituted by one or more xe2x80x94OH, xe2x80x94OE4 or xe2x80x94NH2, or mixtures thereof; or E29 is phenyl or phenylalkyl of 7 to 15 carbon atoms, or said phenyl or said phenylalkyl substituted by one to three alkyl groups of 1 to 4 carbon atoms;
E2 and E9 are independently hydrogen, straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by one to three alkyl of 1 to 4 carbon atoms or by one or more of the following groups xe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94Xxe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n or xe2x80x94Xxe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n; or E2 and E9 are independently said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more xe2x80x94OH, xe2x80x94OCOE11, xe2x80x94OE4, xe2x80x94NCO, xe2x80x94NH2, xe2x80x94NHCOE11, xe2x80x94NHE4 or xe2x80x94N(E4)2, or mixtures thereof, where E4 is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94NE4xe2x80x94 groups or mixtures thereof and which can be unsubstituted or substituted by one or more xe2x80x94OH, xe2x80x94OE4 or xe2x80x94NH2 groups or mixtures thereof; or
E1, E2 and E9 are also independently xe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n or xe2x80x94T1xe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n;
E11 is hydrogen, straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 14 carbon atoms or phenylalkyl of 7 to 15 carbon atoms;
L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, cycloalkylidene of 5 to 12 carbon atoms or xcex1,xcex1,xcex1xe2x80x2,xcex1xe2x80x2-tetramethyl-m-xylylene;
E3 is alkyl of 1 to 20 carbon atoms, said alkyl substituted by alkoxycarbonyl of 2 to 9 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to 16 carbon atoms,
E5 and E8 are independently the same as E2; or E5 and E8 are independently hydrogen, xe2x80x94Xxe2x80x94E1, xe2x80x94Xxe2x80x94COxe2x80x94E2, xe2x80x94Xxe2x80x94COxe2x80x94X1, xe2x80x94Xxe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n or xe2x80x94Xxe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n;
X1 is xe2x80x94NHxe2x80x94E4 or xe2x80x94Xxe2x80x94E2;
with the proviso that at least one of G2, G7, E1, E2, E5, E8 and E9 contains a group xe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94Xxe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n or xe2x80x94Xxe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n; where T1 and T2 are independently alkylene of 1 to 18 carbon atoms or alkylene-phenylene-alkylene of 8 to 20 carbon atoms, and R1 and R2 are independently alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 10 carbon atoms or phenylalkyl of 7 to 20 carbon atoms, preferably alkyl of 1 to 3 carbon atoms or phenyl, and n is 0, 1, 2 or 3.
Preferably, the new benzotriazole is a compound of formula IA or IIA 
wherein
G1 and G6 are hydrogen,
G2 and G7 are independently cyano, CF3xe2x80x94, fluoro, xe2x80x94COxe2x80x94G3 or E3SO2xe2x80x94, or G7 is also hydrogen,
G3 is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,
E1 is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,
E2 and E9 are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; or E2 is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more xe2x80x94OH, xe2x80x94OCOE11, xe2x80x94OE4, xe2x80x94NCO, xe2x80x94NH2, xe2x80x94NHCOE11, xe2x80x94NHE4 or xe2x80x94N(E4)2, or mixtures thereof, where E4 is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94NE4xe2x80x94 groups or mixtures thereof and which can be unsubstituted or substituted by one or more xe2x80x94OH, xe2x80x94OE4 or xe2x80x94NH2 groups or mixtures thereof;
E11 is hydrogen, straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 14 carbon atoms or phenylalkyl of 7 to 15 carbon atoms;
E3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to 16 carbon atoms;
L is methylene; and
with the proviso that at least one of E1, E2 and E9 contains a group xe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94Xxe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n or xe2x80x94Xxe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n;
where T1 and T2 are independently alkylene of 2 or 3 carbon atoms, and R1 and R2 are independently alkyl of 1 to 6 carbon atoms or phenyl, and n is 0, 1, 2 or 3.
Another preferred embodiment of the instant invention is a compound of formula IA 
wherein
G1 is hydrogen,
G2 is CF3xe2x80x94, fluoro or E3SO2xe2x80x94,
E1 is hydrogen or straight or branched alkyl of 2 to 24 carbon atoms,
E2 is as defined above, and
E3 is straight or branched chain alkyl of 1 to 7 carbon atoms,
with the proviso that E2 contains a group xe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94T1xe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n, xe2x80x94Xxe2x80x94T1xe2x80x94Si(OR2)n(R1)3-n or xe2x80x94Xxe2x80x94T1xe2x80x94Xxe2x80x94COxe2x80x94Xxe2x80x94T2xe2x80x94Si(OR2)n(R1)3-n; where T1 and T2 are independently alkylene of 2 or 3 carbon atoms, and R1 and R2 are independently alkyl of 1 to 6 carbon atoms or phenyl, and n is 0, 1, 2 or 3.
Preferably, the compound of formula (I) is
(a) 5-trifluoromethyl-2-[2-hydroxy-3-(3-triethoxysilyl)propyl-5-tert-octylphenyl]-2H-benzo-triazole;
(b) 5-trifluoromethyl-2-{2-hydroxy-3-tert-butyl-5-[3-(3-triethyoxysilyl)propylcarbamoyloxy)-propyl]phenyl}2H-benzotriazole;
(c) 5-trifluoromethyl-2-{2-hydroxy-3-tert-butyl-5-[2-(3-triethyoxysilyl)propylcarbamoyl-oxy)ethyl]phenyl}-2H-benzotriazole;
(d) 5-trifluoromethyl-2-{2-hydroxy-5-[2-(3-triethyoxysilyl)propyl-carbamoyloxy)ethyl]-phenyl}-2H-benzotriazole;
(e) 5-trifluoromethyl-2-{2-hydroxy-3-xcex1-cumyl-5-[2-(3-triethyoxysilyl)propylcarbamoyl-oxy)ethyl]phenyl}-2H-benzotriazole;
(f) 5-trifluoromethyl-2-{2-hydroxy-3-tert-butyl-5-[2-(3-(diethoxymethylsilyl)propylamino-carbonylethyl]phenyl}-2H-benzotriazole;
(g) 5-phenylsulfonyl-2-{2-hydroxy-3-tert-butyl-5-[3-(2-ethoxydimethylsilyl)ethylcarbonyl-oxy)propyl]phenyl}-2H-benzotriazole;
(h) 5-n-butylsulfonyl-2-{2-hydroxy-3-tert-butyl-5-[2-(3-ethoxydimethylsilyl)propyl-oxycarbonyl)ethyl]phenyl}-2H-benzotriazole;
(i) 5-trifluoromethyl-2-[2-hydroxy-3-(ethoxydimethylsilyl)propyl-5-tert-octylphenyl]-2H-benzotriazole;
(j) 5-trifluoromethyl-2-[2-hydroxy-3-(trimethylsilyl)propyl-5-tert-butylphenyl]-2H-benzo-triazole;
(k) 5-[3-(diethoxyethylsilyl)propoxycarbonyl]-2-(2-hydroxy-3-xcex1-cumyl-5-tert-octyl-phenyl)-2H-benzotriazole;
(l) 5-[3-(diethoxyethylsilyl)propylaminocarbonyl]-2-(2-hydroxy-3-xcex1-cumyl-5-tert-octyl-phenyl)-2H-benzotriazole; 
The instant invention also pertains to a composition stabilized against light-induced degradation which comprises,
(a) an organic material subject to light-induced degradation, and
(b) an effective stabilizing amount of a compound of formula (I) or (II).
Preferably, the organic material is a natural, semi-synthetic or synthetic polymer, especially a thermoplastic polymer.
Most preferably, the polymer is a polyolefin or polycarbonate, especially polyethylene or polypropylene; most especially polypropylene; or the polymer is a styrenic, ABS, a nylon, a polyester such as poly(ethylene terephthalate) or poly(butylene terephthalate), a polyurethane, an acrylate, a rubber modified styrenic, poly(vinyl chloride), poly(vinyl butyral), polyacetal (polyoxymethylene), poly(ethylene naphthalenedicarboxylate), or other blends or copolymers such as poly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETG or an ionomer.
Most especially, the polymer is a siloxane coating as a screening layer over polycarbonate.
In another preferred embodiment of the instant invention, the organic material is a resin selected from the group consisting of a thermoset acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modified acrylic melamine, an acrylic resin with carbamate pendant groups crosslinked with melamine or an acrylic polyol resin crosslinked with melamine containing carbamate groups.
Such automotive coatings are described in WO 92/20726; WO 92/05225 and by H. Furakawa et al., Progress in Organic Coatings, 24, 81-99 (1994) which describe the curing and properties of acrylosilane coatings.
Most preferably, the resin is a thermoset acrylic melamine resin or an acrylic urethane resin.
In yet another preferred embodiment of the instant invention, the organic material is a recording material.
The recording materials according to the invention are suitable for pressure-sensitive copying systems, photocopying systems using microcapsules, heat-sensitive copying systems, photographic materials and ink jet printing.
The recording materials according to the invention are distinguished by an unexpected improvement in quality, especially with regard to the fastness to light.
The recording materials according to the invention have the construction known for the particular use. They consist of a customary carrier, for example, paper or plastic film, which has been coated with one or more layers. Depending on the type of material, these layers contain the appropriate necessary components, in the case of photographic materials, for example, silver halide emulsions, dye couplers, dyes and the like. Material particularly suitable for ink jet printing has a layer particularly absorptive for ink on a customary carrier. Uncoated paper can also be employed for ink jet printing. In this case the paper acts at the same time as the carrier material and as the ink-absorbent layer. Suitable material for ink jet printing is, for example, described in U.S. Pat. No. 5,073,448 which is incorporated herein by reference.
The recording material can also be transparent as, for example, in the case of projection films.
The compounds of formula (I) or (II) can be incorporated into the carder material as early as the production of the latter, in the production of paper, for example, being added to the paper pulp. A second method of application is to spray the carder material with an aqueous solution of compounds of formula (I) or (II) or to add the compounds to the coating composition.
Coating compositions intended for transparent recording materials suitable for projection cannot contain any particles which scatter light, such as pigments and fillers.
The dye-binding coating composition can contain a number of other additives, for example, antioxidants, light stabilizers (including also UV absorbers which do not fall under the scope of the UV absorbers of this invention), viscosity improvers, fluorescent brighteners, biocides and/or antistatic agents.
The coating composition is usually prepared as follows: the water-soluble components, for example, the binder, are dissolved in water and stirred together; the solid components, for example, fillers and other additives already described, are dispersed in this aqueous medium; and disperison is advantageously carried out by means of devices, for example, ultrasonic systems, turbine stirrers, homogenizers, colloid mills, bead mills, sand mills, high-speed stirrers and the like. The compounds of formula (I) or (II) can be easily incorporated into the coating composition.
The recording material according to this invention preferably contains 1 to 5000 mg/m2, in particular 50-1200 mg/m2, of a compound of formula (I) or formula (II).
As already mentioned, the recording materials according to the invention embrace a wide field. The compounds of formula (I) or (II) can, for example, be employed in pressure-sensitive copying systems. They can be introduced either into the paper in order to protect the microencapsulated dye precursors there from light, or into the binder of the developer layer in order to protect the dyes formed there.
Photocopying systems using light-sensitive microcapsules which are developed by means of pressure are described in U.S. Pat. Nos. 4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,535,463; 4,551,407; 4,562,137 and 4,608,330; and also in EP-A 139,479; EP-A 162,664; EP-A 164,931; EP-A 237,024; EP-A 237,025 and EP-A 260,129. In all these systems, the compounds can be put into the dye-receiving layer. The compounds can, however, also be put into the donor layer in order to protect the color formers from light.
Photographic materials which can be stabilized are photographic dyes and layers containing such dyes or precursors thereof, for example, photographic paper and films. Suitable materials are, for example, described in U.S. Pat. No. 5,364,749 which is incorporated herein by reference. The compounds of formula (I) or (II) act here as a UV filter against electrostatic flashes. In color photographic materials, couplers and dyes are also protected against photochemical decomposition.
The instant compounds can be used for all types of color photographic materials. For example, they can be employed for color paper, color reversal paper, direct-positive color material, color negative film, color positive film, color reversal film and the like. They are preferably used inter alia for photographic color material which contains a reversal substrate or form positives.
Color-photographic recording materials usually contain, on a support, a blue-sensitive and/or a green-sensitive and/or a red-sensitive silver halide emulsion layer and, if desired, a protection layer, with the instant compounds being, preferably, either in the green-sensitive or the red-sensitive layer or in a layer between the green-sensitive and the red-sensitive layer or in a layer on top of the silver halide emulsion layers.
The compounds of formula (I) or (II) can also be employed in recording materials based on the principles of photopolymerization, photoplasticization or the rupture of microcapsules, or in cases where heat-sensitive and light-sensitive diazonium salts, leuko dyes having an oxidizing agent or dye lactones having Lewis acids are used.
Furthermore, the instant compounds can be employed in recording materials for dye diffusion transfer printing, thermal wax transfer printing and non-matrix printing and for use with electrostatic, electrographic, electrophoretic, magnetographic and laser-electrophotographic printers and pen-plotters. Of the above, recording materials for dye diffusion transfer printing are preferred, for example, as described in EP-A 507,734.
The instant compounds can also be employed in inks, preferably for ink jet printing, for example, as described in U.S. Pat. No. 5,098,477 which is incorporated herein by reference.
The compounds of this invention exhibit superior hydrolytic stability, handling and storage stability as well as good resistance to extractability when present in a stabilized composition.
The methodology to make the instant compounds is described in the prior art. The intermediates needed to make the instant compounds are largely items of commerce.
In general polymers which can be stabilized include
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE). Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated temperature).
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either xcfx80- or "sgr"-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PPILDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/iso-butylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethyleneloctene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylenelalkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid co-polymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon mon-oxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(xcex1-methylstyrene).
6. Copolymers of styrene or xcex1-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrenelethylene/propylene/styrene.
7. Graft copolymers of styrene or xcex1-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylo-nitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from xcex1,xcex2-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.
29. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for example, in U.S. Pat. No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.
32. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins. The unsaturated acrylic resins include the urethane acrylates, polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and the acrylated melamines. The polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.
33. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.
34. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an epoxy functional coetherified high solids melamine resin such as LSE-4103 (Monsanto).
In general, the compounds of the present invention are employed in from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is from about 0.05 to about 3%, and especially 0.05 to about 1%. However, some high performance films or in UV absorbing layers of laminates such as those produced by coextrusion may contain from 5-15% by weight of the instant compounds. Concentrations of 5-10% by weight are typical in certain coextrusion applications.
The stabilizers of the instant invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The resulting stabilized polymer compositions of the invention may optionally also contain from about 0.01 to about 5%, preferably from about 0.025 to about 2%, and especially from about 0.1 to about 1% by weight of various conventional additives, such as the materials listed below, or mixtures thereof.
1. Antioxidants
1.1. Alkylated Monophenols, for Example,
2,6-di-tert-butyl-4-methylphenol
2-tert-butyl-4,6-dimethylphenol
2,6-di-tert-butyl-4-ethylphenol
2,6-di-tert-butyl-4-n-butylphenol
2,6-di-tert-butyl-4-i-butylphenol
2,6-di-cyclopentyl-4-methylphenol
2-(xcex1-methylcyclohexyl)4,6-dimethylphenol
2,6-di-octadecyl-4-methylphenol
2,4,6-tri-cyclohexylphenol
2,6-di-tert-butyl-4-methoxymethylphenol
1.2. Alkylated Hydroquinones, for Example,
2,6-di-tert-butyl-4-methoxyphenol
2,5-di-tert-butyl-hydroquinone
2,5-di-tert-amyl-hydroquinone
2,6-diphenyl-4-octadecyloxyphenol
1.3. Hydroxylated Thiodiphenyl Ethers, for Example,
2,2xe2x80x2-thio-bis-(6-tert-butyl-4-methyl phenol)
2,2xe2x80x2-thio-bis-(4-octylphenol)
4,4xe2x80x2-thio-bis-(6-tert-butyl-3-methylphenol)
4,4xe2x80x2-thio-bis-(6-tert-butyl-2-methylphenol)
1.4. Alkylidene-bisphenols, for Example,
2,2xe2x80x2-methylene-bis-(6-tert-butyl-4-methylphenol)
2,2xe2x80x2-methylene-bis-(6-tert-butyl-4-ethylphenol)
2,2xe2x80x2-methylene-bis-[4-methyl-6-(xcex1-methylcyclohexyl)-phenol]
2,2xe2x80x2-methylene-bis-(4-methyl-6-cyclohexylphenol)
2,2xe2x80x2-methylene-bis-(6-nonyl-4-methylphenol)
2,2xe2x80x2-methylene-bis-[6-(xcex1-methylbenzyl)4-nonylphenol]
2,2xe2x80x2-methylene-bis-[6-(xcex1,xcex1-dimethylbenzyl)4-nonylphenol]
2,2xe2x80x2-methylene-bis-(4,6-di-tert-butylphenol)
2,2xe2x80x2-ethylidene-bis-(4,6-di-tert-butylphenol)
2,2xe2x80x2-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)
4,4xe2x80x2-methylene-bis-(2,6-di-tert-butylphenol)
4,4xe2x80x2-methylene-bis-(6-tert-butyl-2-methylphenol)
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane
2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol
1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane
ethyleneglycol bis-[3,3-bis-(3xe2x80x2-tert-butyl-4xe2x80x2-hydroxyphenyl)-butyrate]
di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene
di-[2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.
1.5. Benzyl Compounds, for Example,
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene
di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide
3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester
bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate
1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium-salt
1.6. Acylaminophenols, for Example,
4-hydroxy-lauric acid anilide
4-hydroxy-stearic acid anilide
2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine
octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate
1.7. Esters of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols, for example,
1.8. Esters of xcex2-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols, for example,
1.9. Amides of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid for example,
N,Nxe2x80x2-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine
N,Nxe2x80x2-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine
N,Nxe2x80x2-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine
1.10 Diarylamines, for example,
diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, 4,4xe2x80x2-di-tert-octyl-diphenylamine, reaction product of N-phenylbenzylamine and 2,4,4-trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.
2. UV Absorbers and Light Stabilizers
2.1. 2-(2xe2x80x2-Hydroxyphenyl)-benzotriazoles, for example, the 5xe2x80x2-methylxe2x80x94, 3xe2x80x2,5xe2x80x2-di-tert-butylxe2x80x94, 5xe2x80x2-tert-butyl-, 5xe2x80x2-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3xe2x80x2,5xe2x80x2-di-tert-butyl-, 5-chloro-3xe2x80x2-tert-butyl-5xe2x80x2-methyl-, 3xe2x80x2-sec-butyl-5xe2x80x2-tert-butyl-, 4xe2x80x2-octoxy, 3xe2x80x2,5xe2x80x2-di-tert-amyl-, 3xe2x80x2,5xe2x80x2-bis-(xcex1,xcex1-dimethylbenzyl), 3xe2x80x2-tert-butyl-5xe2x80x2-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-, 3xe2x80x2-dodecyl-5xe2x80x2-methyl-, and 3xe2x80x2-tert-butyl-5xe2x80x2-(2-octyloxycarbonyl)ethyl-, and dodecylated-5xe2x80x2-methyl derivatives.
2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2xe2x80x2,4xe2x80x2-trihydroxy- and 2xe2x80x2-hydroxy-4,4xe2x80x2-dimethoxy derivatives.
2.3. Esters of optionally substituted benzoic acids for example, phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.
2.4. Acrylates, for example, xcex1-cyano-xcex2,xcex2-diphenylacrylic acid ethyl ester or isooctyl ester, xcex1-carbomethoxy-cinnamic acid methyl ester, xcex1-cyano-xcex2-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, xcex1-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(xcex2-carbomethoxy-xcex2-cyanovinyl)-2-methyl-indoline.
2.5. Nickel compounds, for example, nickel complexes of 2,2xe2x80x2-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol]such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyidithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.
2.6. Sterically hindered amines, for example bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid bis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,Nxe2x80x2-(2,2,6,6-tetra-methylpiperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,1xe2x80x2(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone), bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
2.7. Oxalic acid diamides, for example, 4,4xe2x80x2-di-octyloxy-oxanilide, 2,2xe2x80x2-di-octyloxy-5,5xe2x80x2-di-tert-butyl-oxanilide, 2,2xe2x80x2-di-dodecyloxy-5,5xe2x80x2-di-tert-butyl-oxanilide, 2-ethoxy-2xe2x80x2-ethyl-oxanilide, N,Nxe2x80x2-bis (3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2xe2x80x2-ethyloxanilide and its mixture with 2-ethoxy-2xe2x80x2-ethyl-5,4xe2x80x2-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.
2.8. Hydroxyphenyl-s-triazines, for example 2,6-bis-(2,4-dimethylphenyl)4-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine; 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.
3. Metal deactivators, for example, N,Nxe2x80x2-diphenyloxalic acid diamide, N-salicylalxe2x80x94Nxe2x80x2-salicyloyl-hydrazine, N,Nxe2x80x2-bis-salicyloylhydrazine, N,Nxe2x80x2-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, 3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic acid dihydrazide.
4. Phosphites and phosphonites, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyidialkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, di-isodecyl-pentaerythritol diphosphite, di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite, di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite, di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl) 4,4xe2x80x2-diphenylylenediphosphonite.
5. Compounds which destroy peroxide, for example, esters of xcex2-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis-(xcex2-dodecylmercapto)-propionate.
6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxyl-amine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
8. Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipic acid, diphenylacetic acid.
11. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
12. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, anti-static agents, blowing agents and thiosynergists such as dilauryl thiodipropionate or distearyl thiodipropionate.
13. Benzofuranones and indolinones, for example those disclosed in U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312, or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3xe2x80x2-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-di-methyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
The co-stabilizers, with the exception of the benzofuranones listed under 13, are added for example in concentrations of 0.01 to 10%, relative to the total weight of the material to be stabilized.
Further preferred compositions comprise, in addition to components (a) and (b) further additives, in particular phenolic antioxidants, light stabilizers or processing stabilizers.
Particularly preferred additives are phenolic antioxidants (item 1 of the list), sterically hindered amines (item 2.6 of the list), phosphites and phosphonites (item 4 of the list), UV absorbers (item 2 of the list) and peroxide-destroying compounds (item 5 of the list).
Additional additives (stabilizers) which are also particularly preferred are benzofuran-2-ones, such as described, for example, in U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.
The phenolic antioxidant of particular interest is selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2xe2x80x2-ethylidene-bis(4,6-di-tert-butylphenol), 1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate, 1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris-[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,Nxe2x80x2-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,Nxe2x80x2-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-eth yl]-oxamide.
A most preferred phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-tri-methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2xe2x80x2-ethylidene-bis(4,6-di-tert-butylphenol).
The hindered amine compound of particular interest is selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione, tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin4-yl)ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2] heneicosane, polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4xe2x80x2-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), polycondensation product of I-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, polycondensation product of 4,4xe2x80x2-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4xe2x80x2-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-y l]-1,10-diamino4,7-diazadecane, mixed [2,2,6,6-tetramethylpiperidin-4-yl/xcex2,xcex2,xcex2xe2x80x2,xcex2xe2x80x2-tetramethyl-3,9-(2,4,8, 10-tetraoxaspiro[5.5]-undecane) diethyl] 1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethylpiperidin-4-yl/xcex2,xcex2,xcex2xe2x80x2,xcex2xe2x80x2-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethyl] 1,2,3,4-butanetetracarboxylate, octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate), 4,4xe2x80x2-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one), N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide, N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)imino], 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine, and 1-(2-hydroxy-2-ethylpropoxy-4-octadecanoyloxy-2,2,6,6-tetramethyl-piperidine.
A most preferred hindered amine compound is bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4xe2x80x2-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino4,7-diazadecane, di-(1-octyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino], 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)-n-butylamino]-s-triazine, or 1-(2-hydroxy-2-ethylpropoxy-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.
The instant composition can additionally contain another UV absorber selected from the group consisting of the benzotriazoles, s-triazines, the oxanilides, the benzylidene malonates, the hydroxybenzophenones, benzoates and the xcex1-cyanoacrylates.
Particularly, the instant composition may additionally contain an effective stabilizing amount of at least one other 2-hydroxyphenyl-2H-benzotriazole; a tris-aryl-s-triazine; or a hindered amine or mixtures thereof.
Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from the group consisting of
2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
2-[2-hydroxy-3,5-di(xcex1,xcex1-dimethylbenzyl)phenyl]-2H-benzotriazole;
2-[2-hydroxy-3-(xcex1,xcex1-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;
2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole;
5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;
5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;
2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;
2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl)2H-benzotriazole;
5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;
5-trifluoromethyl-2-(2-hydroxy-3,5di-tert-octylphenyl)-2H-benzotriazole;
2,2xe2x80x2-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol];
methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2xe2x80x2-[4-tert-octyl-6-(5-trifluoro-methyl-2H-benzotriazol-2-yl)phenol];
3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid;
methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;
isooctyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;
5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;
5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole;
5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole;
5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzotriazole;
5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole;
5-trifluoromethyl-2-(2-hydroxy-3-xcex1-cumyl-5-tert-butylphenyl)-2H-benzotriazole;
5-trifluoromethyl-2-(2-hydroxy-3-xcex1-cumyl-5-nonylphenyl)-2H-benzotriazole;
5-trifluoromethyl-2-[2-hydroxy-3-xcex1-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;
5-trifluoromethyl-2-[2-hydroxy-3-xcex1-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;
5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-amylphenyl)-2H-benzotriazole;
5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-butylphenyl)-2H-benzotriazole;
5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;
5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;
5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;
5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;
5-trifluoromethyl-2-(2-hydroxy-3,5-di-xcex1-cumylphenyl)-2H-benzotriazole;
5-fluoro-2-(2-hydroxy-3,5-di-xcex1-cumylphenyl)-2H-benzotriazole;
5-butylsulfonyl-2-(2-hydroxy-3,5-di-xcex1-cumylphenyl)-2H-benzotriazole;
5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; and
5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole.
Preferably, the tris-aryl-s-triazine is selected from the group consisting of
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;
2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine; and
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine.
The alkyd resin lacquers which can be stabilized against the action of light and moisture in accordance with the instant invention are the conventional stoving lacquers which are used in particular for coating automobiles (automobile finishing lacquers), for example lacquers based on alkyd/melamine resins and alkyd/acrylicimelamine resins (see H. Wagner and H. F. Sarx, xe2x80x9cLackkunstharzexe2x80x9d (1977), pages 99-123). Other crosslinking agents include glycouril resins, blocked isocyanates or epoxy resins.
The lacquers stabilized in accordance with the invention are suitable both for metal finish coatings and solid shade finishes, especially in the case of retouching finishes, as well as various coil coating applications. The lacquers stabilized in accordance with the invention are preferably applied in the conventional manner by two methods, either by the single-coat method or by the two-coat method. In the latter method, the pigment-containing base coat is applied first and then a covering coat of clear lacquer over it.
It is also to be noted that the compounds of the present invention are applicable for use in non-acid catalyzed thermoset resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicon, isocyanates or isocyanurates. The epoxy and epoxy-polyester resins are crosslinked with conventional crosslinkers such as acids, acid anhydrides, amines and the like. Correspondingly, the epoxide may be utilized as the crosslinking agent for various acrylic or polyester resin systems that have been modified by the presence of reactive groups on the backbone structure.
When used in two-coat finishes, the compounds of the instant invention can be incorporated in the clear coat or both in the clear coat and in the pigmented base coat.
When water-soluble, water miscible or water dispersible coating are desired ammonium salts of acid groups present in the resin are formed. Powder coating composition can be prepared by reacting glycidyl methacrylate with selected alcohol components.
The instant benzotriazoles are made by conventional methods for preparing such compounds. The usual procedure involves the diazotization of a substituted o-nitroaniline followed by coupling the resultant diazonium salt with a substituted phenol and reduction of the azobenzene intermediate to the corresponding desired benzotriazole. The starting materials for these benzotriazoles are largely items of commerce or can be prepared by normal methods of organic synthesis.
While the instant benzotriazoles with their enhanced durability are particularly suited for automotive coating applications, it is contemplated that they will also be especially useful in other applications where their enhanced durability is required such as in solar films and the like.
The following examples are meant for illustrative purposes only and are not to be construed to limit the scope of the instant invention in any manner whatsoever.